1. Field of the Invention
The present invention relates to an addition curing type silicone resin composition useful in a variety of fields including electrical and electronic equipment, OA equipment and precision instruments.
2. Description of the Prior Art
Silicone resins are widely known as resins which display superior properties of heat resistance, cold resistance, electrical insulation, weather resistance, water repellency and transparency, and as such are widely used in a variety of fields including electrical and electronic equipment, OA equipment, motor vehicles, precision instruments, and building materials.
Furthermore in recent years, particularly transparent organic materials have been proposed as a potential alternative to inorganic glass materials in fields such as the manufacture of optical lenses, because they offer superior workability, and are lightweight, low cost and impact resistant. Amongst such transparent organic materials, silicone based resins are superior to other organic materials in terms of transparency and associated optical characteristics, and as such offer one of the most promising alternatives to inorganic glass materials and the like.
Amongst silicone resins, addition curing type silicone resin compositions such as those disclosed in Japanese Laid-open patent publication (kokai) No. 11-1619 (JP11-1619A) offer certain advantages, including being solventless and consequently offering superior moldability to solvent based condensation curing silicone materials such as silicone varnish, and moreover being more environmentally friendly due to the fact that they contain almost no solvent. Furthermore, because of the high degree of moldability they offer, silicone resins are also used in the production of key pads, although to enable their use in small, lightweight devices such as mobile telephones, the key pad member must be very thin, and as a result, further strength improvements in these key pad compositions are required.
However, silicone resin compositions such as those disclosed in Japanese Laid-open patent publication (kokai) No. 11-1619 (JP11-1619A) do not offer sufficient strength to enable their use in the type of applications described above.
In order to resolve the issues described above, an object of the present invention is to provide an addition curing type silicone resin composition which on curing produces a cured product which is transparent, displays good strength, and particularly good flexural strength, and moreover also displays a high degree of hardness.
As a result of intensive investigations aimed at resolving the aforementioned issues, the inventors of the present invention discovered that in order to increase the strength, particularly the flexural strength, and the hardness of a cured product, the cross linking density of the siloxane must be increased, and the xcfx80xe2x80x94xcfx80 interactions between aromatic rings must also be considered as an important factor. The inventors also discovered that the aforementioned object of the present invention could be achieved by addition curing of specific organopolysiloxanes with a phenyl group and an alkenyl group, and specific organohydrogenpolysiloxanes with a phenyl group, and were consequently able to complete the present invention.
In other words, the present invention provides an addition curing type silicone resin composition comprising:
(A) 100 parts by weight of an organopolysiloxane represented by the average composition formula (1):
R1aR2bR3cSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2xe2x80x83xe2x80x83(1)
(wherein, R1 represents a phenyl group, R2 represents an alkenyl group of 2 to 10 carbon atoms, R3 represents a monovalent group selected from the group consisting of monovalent hydrocarbon groups with the exception of a phenyl group and alkenyl groups, a hydroxyl group and alkoxy groups, and a, b and c are positive numbers which satisfy the requirements 0.5xe2x89xa6axe2x89xa61.0, 0.2xe2x89xa6bxe2x89xa60.5, 0.2xe2x89xa6cxe2x89xa60.8 and 1.0 less than a+b+c less than 2.0), which incorporates a phenyl group and at least two alkenyl groups within a single molecule, and in which the combined proportion of Si atoms within xe2x89xa1Sixe2x80x94R2 groups and RSiO3/2 units (wherein, R represents either one of R1 and R3 as defined above) relative to the total number of Si atoms is at least 70 mol %;
(B) 1 to 100 parts by weight of an organohydrogenpolysiloxane represented by the average composition formula (2):
R4dHcR5fSiO(4xe2x88x92dxe2x88x92exe2x88x92f)/2xe2x80x83xe2x80x83(2)
xe2x80x83(wherein, R4 represents a phenyl group, R5 represents a monovalent group selected from the group consisting of monovalent hydrocarbon groups with the exception of a phenyl group, a hydroxyl group and alkoxy groups, and d, e and f are positive numbers which satisfy the requirements 0.4xe2x89xa6dxe2x89xa61.0, 0.5xe2x89xa6exe2x89xa60.8, 0.7xe2x89xa6fxe2x89xa61.2 and 1.8 less than d+e+f less than 3.0), which incorporates a phenyl group and at least two SiH groups within a single molecule; and
(C) an effective quantity of a hydrosilylation reaction catalyst.
As follows is a more detailed description of the present invention.
Constituent (A)
Constituent (A), which is one of the essential constituents of an addition curing type silicone resin composition of the present invention, is an organopolysiloxane represented by the average composition formula (1):
R1aR2bR3cSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2xe2x80x83xe2x80x83(1)
(wherein, R1 represents a phenyl group, R2 represents an alkenyl group of 2 to 10 carbon atoms, R3 represents a monovalent group selected from the group consisting of monovalent hydrocarbon groups with the exception of a phenyl group and alkenyl groups, a hydroxyl group and alkoxy groups, and a, b and c are positive numbers which satisfy the requirements 0.5xe2x89xa6axe2x89xa61.0, 0.2xe2x89xa6bxe2x89xa60.5, 0.2xe2x89xa6cxe2x89xa60.8 and 1.0 less than a+b+c less than 2.0), which incorporates a phenyl group and at least two alkenyl groups within a single molecule, and in which the combined proportion of Si atoms within xe2x89xa1Sixe2x80x94R2 groups and RSiO3/2 units (wherein R represents either R1 or R3) relative to the total number of Si atoms is at least 70 mol %.
In the average composition formula (1), as is evident from the relationship 1.0 less than a+b+c less than 2.0 (namely, 2.0/2 less than (4xe2x88x92axe2x88x92bxe2x88x92c)/2 less than 3.0/2), this organopolysiloxane is a branched type structure or a three dimensional network structure with either one type, or two or more types, of RSiO3/2 units and SiO2 units within the molecule, and the alkenyl group represented by the R2 of the xe2x89xa1Sixe2x80x94R2 group undergoes a hydrosilylation reaction with the hydrogen of the organohydrogenpolysiloxane represented by the average composition formula (2), thereby forming further branching or three dimensional network structures. Values of a, b and c which satisfy the requirement 1.3 less than a+b+c less than 1.7 are preferred. Furthermore, even if this organopolysiloxane incorporates R2SiO3/2 units, the terminals may be blocked with R33SiO1/2 units.
In the average composition formula (1), R1 represents a phenyl group and R2 represents an alkenyl group of 2 to 10 carbon atoms. Examples of suitable alkenyl groups include vinyl groups, allyl groups, propenyl groups, isopropenyl groups and butenyl groups, and of these, vinyl groups are preferred.
Furthermore, in the average composition formula (1), R3 represents a monovalent group selected from the group consisting of monovalent hydrocarbons group with the exception of a phenyl group and alkenyl groups, a hydroxyl group and alkoxy groups. Examples of such hydrocarbon groups, which may be the same or different, include substituted or unsubstituted monovalent hydrocarbons of 1 to 20, and preferably 1 to 10 carbon atoms. Specific examples of such hydrocarbon groups include alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tert-butyl groups and hexyl groups; other saturated hydrocarbon groups including cycloalkyl groups such as cyclohexyl groups; aryl groups excluding phenyl groups such as tolyl groups, xylyl groups and naphthyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; halogen substituted hydrocarbon groups such as 3,3,3-trifluoropropyl groups; and cyano substituted hydrocarbons. Examples of alkoxy groups include unsubstituted alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups and phenoxy groups, as well as alkoxy substituted alkoxy groups such as methoxyethoxy groups and ethoxyethoxy groups. Of these groups, methyl groups, ethyl groups, and propyl groups are particularly preferred.
In the average composition formula (1), the number a, which represents the phenyl group content, should satisfy the requirement 0.5xe2x89xa6axe2x89xa61.0, and preferably the requirement 0.55xe2x89xa6axe2x89xa60.95. If the phenyl group content is less than this range, then the cured product does not achieve the necessary flexural strength or hardness, whereas if the phenyl content is too high, then not only does the cured product not have the necessary flexural strength or hardness, but the increase in the viscosity of the composition also causes a deterioration in the workability.
In the average composition formula (1), the number b, which represents the alkenyl group content, should satisfy the requirement 0.2xe2x89xa6bxe2x89xa60.5, and preferably the requirement 0.25xe2x89xa6bxe2x89xa60.45. If the value of b is less than 0.2, then the reaction cured product does not achieve the necessary flexural strength or hardness, whereas if the value of b is greater than 0.5, then the number of cross linking points becomes too large, and the reaction cured product becomes brittle. Furthermore, because the organopolysiloxane represented by the average composition formula (1) undergoes a hydrosilylation reaction with the organohydrogenpolysiloxane represented by the average composition formula (2) to form a cross linked structure, there must be at least two alkenyl groups within each molecule of the organopolysiloxane represented by the average composition formula (1).
In the average composition formula (1), the number c, which represents the amount of the monovalent group represented by R3, should satisfy the requirement 0.2xe2x89xa6cxe2x89xa60.8, and preferably the requirement 0.25xe2x89xa6cxe2x89xa60.7, in order to ensure that the addition curing type silicone resin composition has a suitable viscosity for ensuring the necessary workability, and moreover has a favorable three dimensional network structure following curing.
In order for a heat cured product of a composition of the present invention to display the necessary degree of strength and hardness, the values of a, b and c must satisfy the conditions described above, and in addition, the combined proportion of Si atoms within xe2x89xa1Sixe2x80x94R2 groups and RSiO3/2 units (wherein, R represents either R1 or R3) relative to the total number of Si atoms in the organopolysiloxane represented by the average composition formula (1), which represents a measure of the cross linking and branching within the cured product, should be at least 70 mol %, and preferably between 75 and 95 mol %.
Constituent (B)
Constituent (B), which is one of the essential constituents of an addition curing type silicone resin composition of the present invention, is an organohydrogenpolysiloxane represented by the average composition formula (2),
R4dHeR5fSiO(4xe2x88x92dxe2x88x92exe2x88x92f)/2xe2x80x83xe2x80x83(2)
(wherein, R4 represents a phenyl group, R5 represents a monovalent group selected from the group consisting of monovalent hydrocarbon groups with the exception of a phenyl group, a hydroxyl group and alkoxy groups, and d, e and f are positive numbers which satisfy the requirements 0.4xe2x89xa6dxe2x89xa61.0, 0.5xe2x89xa6exe2x89xa60.8, 0.7xe2x89xa6fxe2x89xa61.2 and 1.8 less than d+e+f less than 3.0), which incorporates a phenyl group and at least two SiH groups within a single molecule.
In the average composition formula (2), R4 represents a phenyl group, and R5 represents a monovalent group selected from the group consisting of monovalent hydrocarbon groups with the exception of a phenyl group and a hydrogen atom, a hydroxyl group and alkoxy groups. Examples of such hydrocarbon groups, which may be the same or different, include substituted or unsubstituted monovalent hydrocarbons of 1 to 20, and preferably 1 to 10 carbon atoms. Specific examples of such hydrocarbon groups include alkyl groups such as methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tert-butyl groups and hexyl groups; other saturated hydrocarbon groups including cycloalkyl groups such as cyclohexyl groups; aryl groups excluding phenyl groups such as tolyl groups, xylyl groups and naphthyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; halogen substituted hydrocarbon groups such as 3,3,3-trifluoropropyl groups; and cyano substituted hydrocarbons. Examples of alkoxy groups include unsubstituted alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups and phenoxy groups, as well as alkoxy substituted alkoxy groups such as methoxyethoxy groups and ethoxyethoxy groups. Of these groups, methyl groups, ethyl groups, and propyl groups are particularly preferred.
In the average composition formula (2), the number d, which represents the phenyl group content, should satisfy the requirement 0.4xe2x89xa6dxe2x89xa61.0, and preferably the requirement 0.5xe2x89xa6dxe2x89xa61.0. If the value of d is less than 0.4, then the reaction cured product does not achieve the necessary strength, whereas if the value is greater than 1.0, the curability of the composition deteriorates and so the reaction cured product does not achieve the necessary hardness or strength.
In the average composition formula (2), the number e, which represents the amount of silicon atom bonded hydrogen atoms should satisfy the requirement 0.5xe2x89xa6exe2x89xa60.8, and preferably the requirement 0.6xe2x89xa6exe2x89xa60.8. If the value of e is less than 0.5, then the reaction cured product does not achieve the necessary hardness, whereas if the value is greater than 0.8, then not only does the number of cross linking points become too large and the reaction cured product become brittle, but the compatibility with the constituent (A) also deteriorates. Furthermore, the constituent (B) functions as a cross linking agent for the constituent (A), and must consequently incorporate at least two SiH groups within each molecule.
In the average composition formula (2), the number f, which represents the amount of the monovalent group represented by R5, should satisfy the requirement 0.7xe2x89xa6fxe2x89xa61.2, and preferably the requirement 0.8xe2x89xa6fxe2x89xa61.1. If the value of f is less than 0.7, then the hardness of the cured product is insufficient, whereas if the value is greater than 1.2, both the hardness and the strength of the cured product are unsatisfactory.
In the average composition formula (2), the values of d, e and f should also satisfy the requirement 1.8 less than d+e+f less than 3.0, and preferably the requirement 2.0 less than d+e+f less than 2.5. In order to ensure a suitable degree of workability following mixing with the constituent (A), the constituent (B) should preferably be of low viscosity, and provided the requirement 1.8 less than d+e+f less than 3.0 is satisfied, the number of straight chain structures is large and the viscosity can be kept low. This organohydrogenpolysiloxane may also incorporate branched structures within the molecule.
The proportion of the constituent (B) used relative to 100 parts by weight of the constituent (A) should be from 1 to 100 parts by weight, with amounts from 5 to 50 parts by weight being preferred. Furthermore, the amount of silicon atom bonded hydrogen atoms (in other words, SiH groups) within the constituent (B) relative to 1 mol of alkenyl groups within the constituent (A) should be from 0.5 to 3 mols, and preferably from 0.7 to 2.0 mols.
Constituent (C)
The hydrosilylation reaction catalyst of the constituent (C) is a cross linking catalyst which promotes a hydrosilylation reaction between the alkenyl groups of the constituent (A) and the silicon atom bonded hydrogen atoms (in other words, SiH groups) of the constituent (B). Suitable examples include platinum based catalysts such as platinum black, platinum (II) chloride, chloroplatinic acid, reaction products of chloroplatinic acid and mohohydric alcohols, coordination compounds of chloroplatinic acid with olefins, and platinum bisacetoacetate, as well as other platinum group metal catalysts such as palladium based catalysts and rhodium based catalysts. This hydrosilylation reaction catalyst is used in quantities which offer effective catalytic action (so-called catalytic quantity), so that the quantity of the catalyst, calculated in terms of the amount of the metal, is typically 1 to 500 ppm, and preferably 2 to 100 ppm, relative to the amount of the constituent (A).
In a composition of the present invention, in addition to the constituents (A) to (C) described above, other materials such as hydrosilylation control agents for improving the hardness or the pot life, and reactive or unreactive straight chain or cyclic low molecular weight organopolysiloxanes for regulating the hardness and the viscosity may also be added, provided such additions do not impair the effects of the present invention.
Furthermore, inorganic fillers such as finely powdered silica or titanium oxide, as well as pigments, flame retardants, heat resistant materials and oxidation resistant materials may also be added if necessary.
From the viewpoints of curability and workability, an addition curing type silicone resin composition of the present invention should have a viscosity of no more than 500 P, and preferably from 1 to 350 P.
An addition curing type silicone resin composition of the present invention cures rapidly on heating, and following heat curing for two hours at 200xc2x0 C., the cured product displays a flexural strength, measured in accordance with JIS K6911, of at least 29.4 MPa (3.00 kgf/mm2), and a hardness, measured using a Barcol hardness tester in accordance with JIS K7060, of at least 60 at Shore D.
In order to ensure that a cured product of an addition curing type silicone resin composition of the present invention has a Shore D hardness of at least 60, the combined proportion of Si atoms within xe2x89xa1Sixe2x80x94R2 groups and RSiO3/2 units (wherein, R represents either R1 or R3) relative to the total number of Si atoms must be at least 70 mol %, and moreover the number of silicon atom bonded hydrogen atoms relative to each Si atom within the constituent (B) must be within a range from 0.5 to 0.8 (0.5xe2x89xa6exe2x89xa60.8). Furthermore, by setting a Shore D hardness of at least 60 as a required condition, and increasing the phenyl group content of the constituent (A) and the constituent (B), high flexural strength values of at least 29.4 MPa (3.00 kgf/mm2), or where necessary 34.3 MPa or even 39.2 MPa can be achieved.
In order to ensure that a cured product obtained by heat curing of an addition curing type silicone resin composition of the present invention displays the desired transparency, the constituent (A) and the constituent (B) must display good compatibility, the refractive index of both the constituent (A) and the constituent (B) should preferably be from 1.47 to 1.57, and in particular, the difference in the refractive indexes of the constituent (A) and the constituent (B) should preferably be no more than 0.08. A cured product produced by heat curing of a composition containing only this type of constituent (A) and constituent (B), together with a constituent (C), is highly transparent and displays a transmittance of at least 85% at a wavelength of 589 nm.